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Thermochemistry
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What is energy? Energy is the ability to do work or produce heat. The Law of Conservation of Energy: ◦ This law states that can not be created or destroyed only transferred. Two types of energy: ◦ Kinetic ◦ Potential
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Heat is energy transferred from a warmer object to a cooler object. Heat is represented mathematically as q The amount of heat energy required to raise the temperature of one gram of pure water by one degree Celsius is called… a calorie The SI unit for energy is the Joule 1 Joule = 0.2390 calories 1 calorie = 4.184 Joules
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A breakfast of cereal, orange juice, and milk contains 230 Calories. Convert this amount of energy in to Joules. 9.6 x 10 5 J
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Glucose is a simple sugar found in fruit. Burning 1.00 g of glucose releases 15.6 kJ of energy. How many Calories are released? 3.73 Calories An fruit and oatmeal bar contains 142 Calories. Convert this energy to Joules 5.94 x 10 5 A chemical reaction releases 86.5 kJ of heat. How many Calories are released? 20.7 Calories
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The specific heat of any substance is the amount of heat required to raise the temperature of one gram of that substance by 1 degree Celsius. The specific heat of water is: 1 cal/g- o C 4.184 J/g- o C The specific heat of concrete is 0.84 J/g- o C This is why in the summer concrete gets hot and water says cool.
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The specific heat of a substance can be used to calculate the heat energy absorbed or given off when that substance changes temperature. q = (C)(m)(ΔT) remember ΔT = T final – T initial Calculate the heat absorbed by a 5 x 10 3 g block of concrete when its temperature is raised from 20 o C to 26 o C. 25,000 J or 25 kJ
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The temperature of a sample of iron with a mass of 10.0 g changed from 50.4 o C to 25.0 o C and released 114 J. What is the specific heat of iron? 0.449 J/g- o C If the temperature of 34.4 g of ethanol increase from 25.0 o C to 78.8 o C, how much heat has been absorbed buy the ethenol. (C for ethanol is 2.44 J/g- o C) 4.52 x 10 3 J
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A 155 g sample of an unknown substance was heated from 25.0 o C to 40.0 o C. In the process, the substance absorbed 5696 J of energy. What is the specific heat of the substance? 2.45 J/g- o C A 38.8 g piece of metal alloy absorbs 181 J as its temperature increases from 25 o C to 36 o C. What is the alloy’s specific heat? 0.424 J/g- o C
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Thermochemistry is the study of heat changes during chemical reactions or phase changes. When studying thermochemistry we look at two things: System ◦ The system is the specific part of the universe that we are studying. Surroundings ◦ The surroundings are everything else in the universe.
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Enthalpy is defined as the heat content of a system at constant pressure. The change in enthalpy for a reaction is called the enthalpy (heat) of reaction. ΔH rxn ΔH rxn = H products – H reactnats
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A thermochemical equation is a balanced equation that includes the physical states of all reactants and products and the enthalpy change. 4 Fe(s) + 3 O 2 (g) 2 Fe 2 O 3 (s)ΔH = -1625 kJ NH 4 NO 3 (s) NH 4 + (aq) + NO 3 - ΔH = 27 kJ
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Hess’s Law states that if you can add two or more equations to produce a final equation for a reaction than the sum of the enthalpy changes of the individual reactions is the enthalpy change of the overall reaction.
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Calculate ΔH for the reaction 2 H 2 O 2 (l) 2 H 2 O(l) + O 2 (g) 2 H 2 (g) + O 2 (g) 2 H 2 O(l)ΔH = -572 kJ H 2 (g) + O 2 (g) H 2 O 2 (l)ΔH = -188 kJ
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Use equations (a) and (b) to determine ΔH for the following reaction: 2 CO(g) + 2 NO(g) 2 CO 2 (g) + N 2 (g) a) 2 CO(g) + O 2 (g) 2 CO 2 (g) ΔH = -566.0 kJ a) N 2 (g) + O 2 (g) 2NO(g) ΔH = -180.6 kJ
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ΔH for the following reaction is -1789 kJ. Use equation (a) to determine ΔH for reaction (b). 4 Al(s) + 3 MnO 2 (s) 2 Al 2 O 3 (s) + 3 Mn(s) a) 4 Al(s) + 3 O 2 2 Al 2 O 3 (s)ΔH = -3352 kJ b) Mn(s) + O 2 (g) MnO 2 ΔH = ?
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The enthalpy of formation for any reaction is defined as the heat change when all reactants are in their elemental form and only one mole of product is produced. S(s) + 3 F 2 (g) SF 6 ΔH o f = -1220 kJ Sometimes we need to use fractional coefficients. H 2 (g) + F 2 (g) HFΔH o f = -273 kJ
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We can use the enthalpy of formation for components of a reaction to calculate the total enthalpy change of the reaction (ΔH rxn ). H 2 S(g) + 4 F 2 (g) 2 HF(g) + SF 6 (g) a) ½ H 2 (g) + ½ F 2 (g) HF ΔH o f = -273 kJ b) S(s) + 3 F 2 (g) SF 6 ΔH o f = -1220 kJ c) H 2 (g) + S(s) H 2 S(g) ΔH o f = -21 kJ
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Determine ΔH for CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O(l) Using: ΔH o f (CO 2 ) = -394 kJ ΔH o f (H 2 O) = -286 kJ ΔH o f (CH 4 ) = -75 kJ ΔH o f (O 2 ) = 0 kJ
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When things rust the reaction taking place is: 4 Fe(s) + 3 O 2 (g) 2 Fe 2 O 3 (s)ΔH = -1625 kJ Any physical or chemical that occurs with no outside intervention is a spontaneous process. If we reverse the above reaction: 2 Fe 2 O 3 (s) 3 O 2 (g) + 4 Fe(s) ΔH = 1625 kJ This process would be non-spontaneous
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Entropy is a measure of the number of possible ways a system can be configured. If we have a piece of paper cut into 8 different sections there would be 56 different ways we could arrange them. (8 x 7) If we cut the paper into 16 different pieces there would be 240 different ways we could arrange them. (16 x 15) We have increased the papers entropy.
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The second law of thermodynamics states that a spontaneous reaction will always occur in such a way that entropy increases. Remember that the change in enthalpy (ΔH) is defined as: H products – H reactants Similarly: ΔS = S products – S reactants If ΔS is positive the entropy of the system is increasing. If ΔS is negative the entropy of the system is decreasing.
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Phase Changes: ◦ When a phase change occurs from a more ordered state to a less ordered state ΔS will be positive. ◦ Solid Liquid ΔS > 0 ◦ When a phase change occurs from a less ordered state to a more ordered state ΔS will be negative. ◦ Gas LiquidΔS < 0 Dissolving a gas into a solvent always results in a decrease in entropy.
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Assuming no change in physical state, entropy increases when the number of moles of products is greater than the number of moles of reactants. ◦ 2 SO 3 (g) 2 SO 2 (g) + O 2 (g) Entropy increases when a solute dissolves in a solvent. ◦ NaCl(s) Na + (aq) + Cl - (aq) Entropy increases as temperature increases.
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Predict the sign of ΔS for each of the following chemical of physical processes ClF(g) + F 2 (g) ClF 3 (g)ΔS = NH 3 (g) NH 3 (aq)ΔS = Entropy has the units Joules/Kelvin
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Named after physicist J. Willard Gibbs, free energy is the maximum amount of energy available during a chemical reaction. Gibbs Free Energy Equation: ΔG = ΔH – TΔS When a reaction occurs at standard conditions (298 K and 1atm) ΔG o = ΔH o - ΔS o
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ΔG = ΔH – TΔS A reaction where ΔH is negative and ΔS is positive will always be spontaneous. N 2 (g) + 3 H 2 (g) 2 NH 3 (g) ΔH = -91.8 kJΔS = -197 J/k ΔG = ΔG = -33.1 kJ
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ΔHΔSΔGReaction Spontaneity
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For a process ΔH is 145 kJ and ΔS is 322 J/K. Calculate ΔG for this reaction at 298 K. Is it spontaneous?
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